EP1177234A1 - Verfahren zur herstellung von oxycarbonylpolymeren, funktionalisierung, hergestellte polymere und funktionalisierungsagens - Google Patents

Verfahren zur herstellung von oxycarbonylpolymeren, funktionalisierung, hergestellte polymere und funktionalisierungsagens

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Publication number
EP1177234A1
EP1177234A1 EP00925411A EP00925411A EP1177234A1 EP 1177234 A1 EP1177234 A1 EP 1177234A1 EP 00925411 A EP00925411 A EP 00925411A EP 00925411 A EP00925411 A EP 00925411A EP 1177234 A1 EP1177234 A1 EP 1177234A1
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Prior art keywords
polymers
agent
monomer
ppm
chosen
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French (fr)
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EP1177234B1 (de
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Pierre Le Perchec
Roselyne Baudry
Frédéric ALVAREZ
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Centre National de la Recherche Scientifique CNRS
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Centre National de la Recherche Scientifique CNRS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids

Definitions

  • the invention relates to a process for obtaining oxacarbonylated polymers by ring opening and polymerization of monomers comprising at least one cyclic oxacarbonylated function such as a lactone function.
  • initiating agents can be of an anionic nature such as a hydride, a carbanion, an alkoxide, a thiolate or a carboxylate of alkali metal, alkaline earth metal, aluminum, zinc or tin; it can be of nucleophilic nature, uncharged, such as a tertiary amine for the polymerization of ⁇ -propiolactone, or a phosphine; it can also be chosen from protic compounds such as carboxylic acids, alcohols, glycols, or polar functions such as primary and secondary amines and combinations of structures such as alkanolamines, or alternatively from coordination complexes such as those aluminum.
  • protic compounds such as carboxylic acids, alcohols, glycols, or polar functions such as primary and secondary amines and combinations of structures such as alkanolamines, or alternatively from coordination complexes such as those aluminum.
  • the polymerization reaction is carried out in a perfectly anhydrous medium in an inert solvent, at a temperature which must sometimes exceed 150 ° C.
  • the present invention provides a process for obtaining oxacarbonylated polymers from monomers comprising at least one cyclic oxacarbonylated function, and in particular a lactone function, making it possible, under mild reaction conditions, to obtain complete consumption of the starting monomer (s) .
  • a temperature close to room temperature is often sufficient to polymerize certain lactones, the reaction of which requires high temperatures by known methods of polymerization, and on the other hand polymers are obtained which are free of starting monomers and of initiating agent after washing, which makes their isolation very easy and makes it possible to envisage their use in very varied applications, including those where it is essential to have a polymer pure.
  • the process of the invention comprises the following stages: at least one monomer comprising at least one cyclic oxacarbonylated function and an initiating agent is available, the polymerization or copolymerization of said monomer is carried out in bulk or in solution, the initiating agent being chosen from the bicyclic guanidine compounds corresponding to formula (I) or formula (II)
  • one and / or the other of the rings can be substituted, in at least any one of the positions 2, 3, 4, 8, 9 and 10 of the formula (I) or at least one any of positions 2, 3, 7 and 8 of formula (II), by at least one radical chosen from alkyl groups having from 1 to 6 carbon atoms, cycloalkyl groups having from 5 to 7 carbon atoms, hydrocarbon chains of polystyrene.
  • oxacarbonylated function is understood to mean an —O-CO— function included in a cycle, the monomer therefore comprising at least one oxygenated heterocycle.
  • it may be a lactone function.
  • a preferred initiating agent has the formula (I) and is 7H-1,5,7-triaza-bicyclo [4.4.0] dec-5-ene (hereinafter referred to as TBD).
  • TBD 7H-1,5,7-triaza-bicyclo [4.4.0] dec-5-ene
  • the monomer or the monomers ⁇ may comprise at least one lactone function, they are then advantageously chosen from the group consisting of ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, 2,6-dimethyl-1,4-dioxan-2,5-dione (or lactide), and 1,4-dioxan-2,5-dione (or glycolide).
  • the process leads to the production of a homopolymer if only one monomer or a copolymer is available, the latter possibly being a block copolymer or a random copolymer, if at least two different monomers are reacted.
  • the molar ratio of the monomer or monomers to the initiating agent varies from 1 to 500, advantageously from 1 to 200, the reaction is carried out at a temperature varying from 0 ° C to 1 50 ° C, preferably from 50 ° C to 1 20 ° C, the reaction is carried out in bulk; it can also be carried out in a solvent chosen in particular from tetrahydrofuran (THF), toluene, acetone, dibutylether, the reaction time varies from 10 minutes to 12 hours.
  • THF tetrahydrofuran
  • An object of the present invention is an oxacarbonylated polymer capable of being obtained by the production process defined above.
  • the process of the invention also has the advantage of making it possible to functionalize the polymers obtained in situ, directly in the reaction mixture, in order to obtain polymers modified by functionalization, activated or activatable.
  • This functionalization is carried out by means of a functionalizing agent, and depending on the destination of the polymer, this functionalization can be particularly advantageous.
  • biodegradable modified polylactones are obtained after functionalization, having the properties of viscosity modifying agent of organic solvents and aqueous media, including water.
  • a functionalizing agent according to the invention is preferably a molecule or a macromolecule, linear or branched, comprising at least one alcohol or amino function.
  • This agent can be selected from:
  • - pure functionalization compounds such as butanol, ethoxyethanol, pentaerythritol, allylamine, methoxyethylamine, decylamine, ethoxyethanolamine, esters of carboxylic acids
  • - functionalized polymers such as polymers and copolymers, such as alkylene glycol polymers and copolymers, and in particular ethylene glycol polymers and copolymers, in particular ethylene glycol (PEG) and propylene glycol (PPG) copolymers, mixtures of said polymers, mixtures of said copolymers, mixtures of said polymers and copolymers, polyalkylene amines such as Jeffamines ®, polyesters such as polyethylene terephthalate, and mixtures thereof,
  • mixtures of the aforementioned agents for example, one can choose the mixture comprising at least one ethylene glycol oxide polymer and at least one polyglucoside.
  • Gums such as xanthan gum and guar gum, optionally in admixture with another functionalizing agent, such as an alkylene glycol oxide polymer, are particularly advantageous agents.
  • the polymerization and the functionalization can be carried out sequentially or else they can be carried out in situ simultaneously, in bulk or in solvent.
  • the invention relates to a process for obtaining oxacarbonylated polymers, as defined above, according to which a functionalization agent is added to the monomer and to the initiating agent, according to an in situ mode, or a block mode.
  • a functionalization agent is added to the monomer and to the initiating agent, according to an in situ mode, or a block mode.
  • a preferred agent is selected from the agents listed above.
  • the invention also relates to a functionalizing agent for an oxacarbonylated polymer, which comprises at least one gum, such as a xanthan or guar gum. This can also be combined with at least one polymer and / or one copolymer of alkylene glycol oxide such as polymers and copolymers of ethylene glycol oxide (PEG).
  • a functionalized polymer oxacarbonyl obtainable by the process of polymerization and functionalization defined above
  • Another subject of the invention is the use of a bicyclic guanidine compound corresponding to formula (I) or (II) above and described above to initiate the polymerization or copolymerization reaction of monomers comprising at least one cyclic oxacarbonylated function.
  • the bicyclic guanidine compound is TBD.
  • a suitable support is mineral or organic and consists of a resin, a polymer such as a polystyrene, a polypropylene, a copolymer such as a polystyrene / divinylbenzene copolymer, silica, clay, diatomite, zeolite, alumina or aluminosilicate.
  • directly or indirectly it is meant that said agent comprises at least on one of its cycles a radical capable of binding to said support, or else a radical which will be linked to said support by means of a coupling arm .
  • the latter is generally a hydrocarbon chain.
  • deposited is meant that said initiator is adsorbed on an organic or inorganic support.
  • FIG. 1 represents the viscosity (in Pa.s 1 ) of the reaction medium described in Example 1 .5 as a function of time (in second 1 ).
  • FIG. 2 represents the viscosity (in Pa.s) of the reaction medium described in Example 1 .6 as a function of time (in second 1 ).
  • FIG. 3 represents the viscosity (in Pa.s 1 ) of the guar gum before (initial or unmodified guar) and after functionalization (modified guar) of the ⁇ -caprolactone of example 9.5, as a function of the shear gradient ( in second "1 ):
  • FIG. 5 illustrates the rheological behavior of a polycaprolactone after functionalization according to Example 9.6, by representation of the shear stress (in Pa) as a function of the shear gradient (in second 1 ).
  • the crude product is characterized by spectral analyzes and size exclusion chromatography (CES) with THF.
  • CES size exclusion chromatography
  • the NMR analysis indicates the masses characteristic of polycaprolactones at ⁇ in ppm of 1.4 CH 2 ⁇ ; 1.65 CH 2 ( ⁇ , ⁇ ); 2.31 CH 2 ⁇
  • the polymer can be obtained free of traces of initiating agent if necessary, by dissolving the polymer in a solvent such as methylene chloride or toluene, followed by extraction with acidified water. To the viscous mixture, 200 ml of CH 2 CI 2 and 200 ml of an aqueous solution of acetic acid diluted to 2% are added. Decanted and the organic phase is isolated. It is washed with 100 ml of water containing 2% of HCl, then again with pure water, and the organic phase is dried.
  • a solvent such as methylene chloride or toluene
  • the reaction is exothermic and the mixture becomes viscous after fifteen minutes of stirring.
  • the reaction is exothermic and the mixture becomes viscous after fifteen minutes of stirring.
  • the proton NMR analysis indicates a polymolecularity index of 230.
  • the proton NMR analysis indicates a polymolecularity index of 230.
  • the polymerization of ⁇ -caprolactone is carried out for a molar ratio M / l of 1,00, in the discoid air gaps of a rheometrix at the temperature of 80 ° C.
  • the H NMR analysis of the sample gives a polymolecularity index of 98.
  • the polymerization of ⁇ -caprolactone is carried out for a molar ratio M / l of 200, on the discoid air gaps of a rheometrix at the temperature of 1,00 ° C.
  • the rise in viscosity is shown in FIG. 2.
  • the viscous plateau is reached after 4500 seconds of contact.
  • the value of viscosity is then 21 00 Pa.s "1 .
  • the 1 H NMR analysis of the sample gives a polymolecularity index of 1.50.
  • the polymer obtained corresponds to the following formula: - [CO- (C ⁇ H 2 -C ⁇ H 2 -C ⁇ H 2 -C ⁇ H 2 -C ⁇ H 2 )] n .
  • O-CO-CH 2 -CH 2 -CH 2 -CH 2 OH where n represents the polymolecularity index
  • composition of the reaction mixture is as follows: 3.45 g (0.0345 mole) of ⁇ -valerolactone, 0.48 g (0.00345 mole) of TBD in 15 ml of anhydrous THF.
  • the reaction is exothermic and the mixture becomes viscous after fifteen minutes of stirring.
  • reaction conditions are the same as those given in Example 1 .1, with a mixture of 51.3 g of ⁇ -caprolactone (0.45 mole) and 5 g of ⁇ -valerolactone (0.05 mole).
  • the molar ratio M / l is 20.
  • the NMR spectrum of the copolymer obtained shows the absence of the starting monomers and is in accordance with the expected polymer.
  • Example 4 Preparation of a polylactide homopolymer from d, l-lactide (or 2,6-dimethyl-1, 4-dixoxan-2,5-dione)
  • the degree of polymolecularity determined by NMR is 10.
  • the polymer contains less than 3% of residual monomer.
  • the reaction is carried out in solution in THF at 60 ° C. 1.06 g of TBD are placed in 10 ml of solvent, then 33 g of ⁇ -caprolactone dissolved in 30 ml of solvent are added dropwise. The reaction mixture is brought to reflux of THF for 180 minutes with stirring at 500 rpm, then it is poured into 100 ml of water. An emulsion is formed. The reaction solvent is removed and replaced with 100 ml of CH 2 CI 2 . The organic phase is decanted and washed with 100 ml of water containing 2% HCl, then with pure water and the solvent is removed. Polycaprolactone is identified free of monomer.
  • Example 6 Preparation of a random ⁇ -caprolactone-d, l-lactide copolymer
  • the random ⁇ -caprolactone (C) -d, l-lactide (L) copolymer can be represented by CLCLCLCLCLCCLCLL-etc.
  • NMR analysis indicates the masses ⁇ , ⁇ , ⁇ , ⁇ , ⁇ of the polymerized lactone accompanied by the masses characteristic of the polymerized d, l-lactide.
  • the average composition by weight of the copolymer is 50 ⁇ -caprolactone units per 38 d, l-lactide units.
  • the block ⁇ -caprolactone (C) -d, l-lactide (L) copolymer can be represented by CCCCC-LLLLL. The following are introduced into a 100 ml three-necked reactor under nitrogen.
  • the average composition by mass of the copolymer is 42 ⁇ -caprolactone units per 28 (56 OCH (CH 3 ) CO fragments) of d, l-lactide.
  • the reaction is carried out in acetone, solvent for the monomeric glycolide.
  • the composition of the initial mixture is 11.6 g (0.1 mole) of glycolide per 0.458 g (0.0033 mole) of TBD.
  • the molar ratio M / l is 30.
  • the reaction is exothermic and a white precipitate immediately forms at room temperature and the first fractions of TBD added.
  • Acetone is brought to reflux for two hours.
  • the white solid is isolated by filtration and the solvent is evaporated under vacuum.
  • the lactone is mixed with the functionalizing agent and the mixture is homogenized at 80 ° C. After homogenization, the initiating agent is introduced all at once. It is heated for 3 hours at 80 ° C, then one hour at 1 00 ° C and finally an hour and a half at 1 20 ° C. The crude reaction mixture is collected and analyzed.
  • a functionalized ⁇ -polycaprolactone is prepared according to the procedure described in 9.1 with 25 g (0.22 mole) of ⁇ -caprolactone, 2.03 g (0.01 46 mole) of TBD and 1.98 g of ethoxyethanol.
  • the molar ratio M / l is 1 5.
  • the polymer is dissolved in 200 ml of CH 2 CI 2 and 100 ml of water containing 2% HCl.
  • the organic phase is decanted and then washed with 100 ml of water.
  • the solvent is evaporated, the residue is taken up in toluene which is in turn evaporated. A washed sample is isolated.
  • a polycaprolactone modified with PEG 6000 is prepared according to the procedure described in Example 9.1.
  • the monomer / initiator and PEG 6000 / initiator molar ratios are 30 and 0.62 respectively.
  • the initial mixture of 50.6 g (0.44 mole) of ⁇ -caprolactone and 54.6 g of PEG 6000 (9.1 0 "3 mole) is brought to 60 ° C.
  • 2.02 g (1.45 x 1 0 2 mole) of TBD are then added in solid form in a single operation.
  • the reaction is exothermic and the temperature reaches 75 ° C. at 80 ° C p "uring 3 hours and then 1 hour at 00 ° C and finally 1 hour 30 minutes 1 20 ° C. was isolated white crude product which solidified on cooling.
  • We identify the signal at ⁇ 4.2 ppm characteristic of the CH 2 protons of the ester resulting from the coupling of PEG 6000 and polycaprolactone.
  • NMR analysis reveals the structural elements of the polycaprolactone as indicated in Example 1 .1 and a signal
  • the monomer / initiator and guar gum / initiator molar ratios are 30 and 0.62 respectively.
  • the light yellow crude product is isolated, which solidifies on cooling.
  • the NMR analysis reveals the structural elements of the polycaprolactone as indicated in example 1 .1 and a complex series of peaks corresponding to the polyglucosidic guar gum.
  • the grafting is characterized by measuring the viscosity of a modified guar gum suspension shown in FIG. 3.
  • the grafting of the polycaprolactone is visualized by a change in solubility of the modified guar gum which becomes soluble in organic solvents, in particular THF and a change in viscosity, as shown in Figure 4.
  • the viscous behavior of the aqueous solution is demonstrated by rheological measurement on Rhéomat 30.
  • the value of the shear stress measured on a 6% aqueous solution reaches 500 Pa at 10 s of shear frequency.
  • the shear stress curve as a function of the shear frequency shows a shear thinning effect.
  • Example 10 Preparation of polylactones and functionalization, according to a sequence mode
  • the lactone is heated to 80 ° C. After homogenization of the lactone, the initiating agent is added. For polymerization, the mixture is heated for 3 hours at 80 ° C. The functionalizing agent is then added and the mixture is brought to 1,00 ° C. for one hour and to 1,20 ° C. for one and a half hours. The crude reaction mixture is collected and analyzed.
  • a polylactone is prepared according to the procedure described in 1. 1 with 11.4 g (0.1 mole) of ⁇ -caprolactone and 2.78 g (0.02 mole) of TBD.
  • the molar ratio M / l is 20.
  • the reactor, equipped with a coolant, is kept for 3 hours at
  • the viscous polymer is treated with 3.6 g of butanol (0.05 mole).
  • the reaction time is extended by bringing the heating oil bath to 1,00 ° C for one hour, then to 120 ° C for one and a half hours.
  • a polycaprolactone is prepared according to the procedure described in 1.1 with 25 g (0.22 mole) of ⁇ -caprolactone and 2.03 g (0.01 46 mole) of TBD.
  • the molar ratio M / l is 1 5.
  • the reaction is exothermic and the temperature reaches 65 ° C.
  • the medium becomes viscous.
  • the reactor is brought to 80 ° C. for 3 hours.
  • the viscous polymer is treated with 1.98 g of ethoxyethanol (0.022 mole).
  • the reaction time is extended by bringing the heating oil bath to 1,00 ° C for one hour, then to 120 ° C for one and a half hours.
  • the raw sample is taken.
  • the polymer is dissolved in 200 ml of CH 2 CI 2 and 100 ml of water containing 2% HCl.
  • the organic phase is decanted and then washed with 100 ml of water.
  • the solvent is evaporated, the residue is taken up in toluene which is in turn evaporated.
  • a polycaprolactone is prepared in accordance with the procedure described in 1.1 with 25 g (0.22 mole) of ⁇ -caprolactone, 3.04 g (0.022 mole) of TBD.
  • the molar ratio M / l is 1 0.
  • the reaction is exothermic and the temperature reaches 65 ° C.
  • the medium becomes viscous.
  • the reactor is brought 3 hours to
  • reaction time is extended by bringing the heating oil bath to 1,00 ° C for one hour, then to 120 ° C for one and a half hours.
  • the raw sample is taken.
  • the polymer is dissolved in
  • ETUC indicates a polymer free from monomer and allylamine.
  • a polycaprolactone is prepared according to the procedure described in 1.1 with 25 g (0.22 mole) of ⁇ -caprolactone and 3.04 g (0.022 mole) of TBD.
  • the molar ratio M / l is 1/1 0.
  • the reaction is exothermic.
  • the medium becomes viscous.
  • the reactor is brought to 80 ° C. for 3 hours.
  • the viscous polymer is treated with 1.65 g of methoxyethylamine (0.022 mole).
  • the reaction time is extended by bringing the heating oil bath to 1,00 ° C for one hour, then to 120 ° C for one and a half hours.
  • the raw sample is taken.
  • the polymer is dissolved in 200 ml of CH 2 CI 2 and 100 ml of water.
  • the organic phase is decanted and then washed with 100 ml of water.
  • the solvent is evaporated, the residue is taken up in toluene which is in turn evaporated.
  • the end-of-chain CH 2 NMR integration ratio on the polycaprolactone residue indicates a degree of polymolecularity of 6.
  • the CES indicates a polymer free of monomer.
  • a polycaprolactone is prepared with 25 g (0.22 mole) of ⁇ -caprolactone and 0.1 g (0.0073 mole) of TBD.
  • the molar ratio M / l is 30.
  • the reaction is exothermic.
  • the medium becomes viscous.
  • the reactor is brought to 80 ° C. for 3 hours.
  • the viscous polymer is treated with
  • the integration report of the chain end on the polycaprolactone residue indicates a degree of polymerization (determined in CES) of 33, before functionalization, and of 22, after treatment with decylamine.
  • the fixation rate assessed by NMR is 70%.
  • ETUC indicates a monomer-free polymer.
  • a polycaprolactone modified by TEG-200 is prepared according to the sequential mode described in 10.1.
  • the monomer / initiator molar ratio is 30; that of the TEG 200 / initiator is 0.89.
  • 35 g (0.31 mole) of ⁇ -caprolactone are brought to 60 ° C.
  • 1.39 g (0.01 mole) of TBD in solid form are added in a single operation.
  • the reaction is exothermic and the temperature reaches 75 ° C.
  • the temperature is maintained at 80 ° C for three hours.
  • the ⁇ -caprolactone polymerizes and the medium becomes pasty. 1.71 g are added
  • ⁇ 3.64 ppm (multiplet).
  • We identify the signal at ⁇ 4.2 ppm (triplet) characteristic of CH 2 protons ester From the coupling of TEG-200 and polycaprolactone. The complete elimination of the initiator is noted by washing.
  • Example 1 1 Preparation of polylactides and functionalization, in situ
  • the lactide is mixed with the functionalizing agent and the mixture is homogenized at 80 ° C. After homogenization, the initiating agent is introduced all at once. It is heated for 3 hours at 80 ° C, then one hour at 1 00 ° C and finally an hour and a half at 1 20 ° C. The crude reaction mixture is collected and analyzed.
  • TBD 60 ° C and 280 mg (2.01 x 10 mole) of TBD are added.
  • the monomer / initiator and PEG 1000 / initiator molar ratios are 25 and 0.40, respectively.
  • a white brittle solid is isolated.
  • NMR analysis indicates the presence of a lactide - PEG coupling ester group and polylactide / OH chain end / COOH chain end ratios of 0.035 / 0.038 / 0.032.
  • the internal temperature of the mixture is brought to 60 ° C. and
  • the procedure is carried out according to a modified procedure of Example 11-1.
  • the initial mixture contains 3.5 g (2.2x10 "2 mole) of (D, L) -lactide and 4 g of
  • PEG 10000 (0.4x10 3 mole). The mixture is brought to 60 ° C. and 0.28 g is added. (2 x 1 0 3 mole) of initiating TBD. The polymerization-grafting reaction is completed according to the protocol of Example 1 .1. The temperature is brought back to 50 ° C. at the end of the reaction and 2.2 g (1.9 ⁇ 10 ⁇ 2 mole) of glycolide are added which react instantly. The mixture is maintained at 80 ° C. for 30 min and the solid is isolated. hard and brittle slightly yellow.
  • the block polymer is poorly soluble in organic solvents, it dissolves in chloroform and DMSO when hot.
  • Example 12 Preparation of polylactides and functionalization, according to a sequence mode
  • the lactide is heated to 80 ° C. After homogenization of the lactone, the initiating agent is added. For polymerization, the mixture is heated for 3 hours at 80 ° C. The functionalizing agent is then added and the mixture is brought to 1,00 ° C. for one hour and to 1,20 ° C. for one and a half hours. The crude reaction mixture is collected and analyzed.
  • Example 1 2.2 illustrates the application of this protocol to obtaining functionalized polylactides.
  • Example 1 2.1 The procedure is the same as that described in Example 1 2.1, with 2.88 g (0.02 mole) of lactide, 185 mg of TBD and 1.8 g of ethoxyethanol (0.02 mole).
  • the molar ratio M / l is 1 5.
  • the addition of the initiating agent at one time causes the solubilization and an increase in temperature up to 38 ° C. After two hours of reaction at 90 ° C, the solution is slightly reddish-brown. The raw sample is analyzed and the sample is washed as before.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Polymerisation Methods In General (AREA)
EP00925411A 1999-05-07 2000-05-05 Verfahren zur herstellung von oxycarbonylpolymeren, funktionalisierung, hergestellte polymere und funktionalisierungsagens Expired - Lifetime EP1177234B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
FR9906039 1999-05-07
FR9906039A FR2793250B1 (fr) 1999-05-07 1999-05-07 Procede d'obtention de polymeres oxacarbonyles et utilisation d'un compose de guanidine bicyclique comme agent initiateur de polymerisation
FR0002864A FR2793251B1 (fr) 1999-05-07 2000-03-06 Procede d'obtention de polymeres oxacarbonyles, fonctionnalisation, polymeres obtenus et agents de fonctionnalisation
FR0002864 2000-03-06
PCT/FR2000/001235 WO2000068293A1 (fr) 1999-05-07 2000-05-05 Procede d'obtention de polymeres oxacarbonyles, fonctionnalisation, polymeres obtenus et agents de fonctionnalisation

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EP1177234A1 true EP1177234A1 (de) 2002-02-06
EP1177234B1 EP1177234B1 (de) 2009-08-05

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JP (1) JP4503860B2 (de)
AT (1) ATE438674T1 (de)
AU (1) AU4414300A (de)
CA (1) CA2373215C (de)
DE (1) DE60042683D1 (de)
FR (1) FR2793251B1 (de)
WO (1) WO2000068293A1 (de)

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DE102004026904A1 (de) * 2004-06-01 2005-12-22 Basf Ag Hochfunktionelle, hoch- oder hyperverzweigte Polyester sowie deren Herstellung und Verwendung
JP2008163073A (ja) * 2006-12-27 2008-07-17 Musashino Chemical Laboratory Ltd 脂肪族ポリエステルの製造方法
AU2009293001B2 (en) * 2008-09-18 2014-12-04 The Curators Of The University Of Missouri Bionanocomposite for tissue regeneration and soft tissue repair
EP2196486A1 (de) * 2008-12-12 2010-06-16 Total Petrochemicals Research Feluy Verfahren zur Herstellung von Di- und Multiblock-Copolymeren
US9388275B2 (en) * 2009-06-01 2016-07-12 International Business Machines Corporation Method of ring-opening polymerization, and related compositions and articles
US8309618B2 (en) * 2009-07-01 2012-11-13 International Business Machines Corporation Catalytic depolymerization of polymers containing electrophilic linkages using nucleophilic reagents
US8367796B2 (en) * 2009-07-01 2013-02-05 International Business Machines Corporation Catalytic polymerization of polymers containing electrophilic linkages using nucleophilic reagents
FI20115504A0 (fi) 2011-05-23 2011-05-23 Teknologian Tutkimuskeskus Vtt Oy Menetelmä glykolidipolyesterin valmistamiseksi renkaanavauspolymeroinnilla
CN107090079A (zh) * 2017-05-26 2017-08-25 南京大学 一种聚乳酸‑聚乙二醇单甲醚双嵌段共聚物及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1016394A (en) * 1961-09-27 1966-01-12 Sumitomo Chemical Co Improvements in or relating to ª‰-propiolactone polymers
NZ205646A (en) * 1982-09-25 1985-04-30 Bp Chem Int Ltd Preparation of alkyl esters of formic acid
GB8401919D0 (en) * 1984-01-25 1984-02-29 Bp Chem Int Ltd Transesterification process
US5359026A (en) * 1993-07-30 1994-10-25 Cargill, Incorporated Poly(lactide) copolymer and process for manufacture thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0068293A1 *

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ATE438674T1 (de) 2009-08-15
JP4503860B2 (ja) 2010-07-14
CA2373215C (fr) 2010-11-16
US6646103B1 (en) 2003-11-11
JP2002544302A (ja) 2002-12-24
DE60042683D1 (de) 2009-09-17
FR2793251A1 (fr) 2000-11-10
EP1177234B1 (de) 2009-08-05
CA2373215A1 (fr) 2000-11-16
FR2793251B1 (fr) 2003-09-05
WO2000068293A1 (fr) 2000-11-16
AU4414300A (en) 2000-11-21

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